JP2527428B2 - Liquid detergent composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to clear and stable liquid detergents such as those used in dishwashing. More specifically, the present invention contains a high level of detergent / surfactant ingredients, but does not contain any conventional non-detergent solubilizers or hydrotropes to achieve clarity or stability. Liquid detergent composition.

PRIOR ART Liquid detergent compositions containing sodium dodecylbenzene sulfonate and ammonium alkyl ether sulphate are known, for example from US Pat. No. 3,231,504. However, in order to formulate a composition containing these detergent active compounds at an acceptable high level, it is necessary to include relatively multiple solubilizers or hydrotropes.
Lower aliphatic alcohols (eg ethyl alcohol), urea, alkylbenzene sulfonates (eg sodium xylene sulfonate) are typical examples of solubilizers and hydrotropes.

Various improvements to these liquid detergent compositions have been made by replacing all or part of the higher alkylbenzene sulfonate detergent with paraffin sulfonate anion detergent. For example, British Patent Specification B 1,339,069 (Corrected Specification) (issued November 28, 1973) and its corresponding US Pat. No. 3,755,206, and US Pat. No. 3,8.
Reference may be made to 12,042 and British Patent Specification 1,567,421. All of the formulations described in these patents still require the addition of hydrotropes or solubilizers referred to as "viscosity and transparency control systems" to achieve the desired clarity and concentration. Therefore, viscosity and transparency control systems (typically ethyl alcohol and / or
Alternatively, the relative concentration of detergent active compounds is necessarily reduced by the amount of space (or mixture of propyl alcohol and urea) occupying the composition. That is, the viscosity and transparency control system does not contribute to the overall cleaning performance of the liquid detergent composition.

Other paraffin sulfonate-based liquid detergent compositions are disclosed in U.S. Pat. No. 4,040,989 and British Patent Specification No.
No. 1,458,798 and No. 1,458,783, all of which are relatively special and expensive nonionic detergent compounds such as mixed ethylene oxide-propylene oxide condensates, 3
Require primary amine oxides, alkanoic acid alkanolamides, etc.

SUMMARY OF THE INVENTION Accordingly, it would be highly desirable, and also desirable, to make further improvements to prior art paraffin sulfonate-based transparent, stable liquid detergent compositions. It is an object of the invention.

In more detail the object of the present invention is a paraffin sulphonate-based transparent, stable liquid detergent composition containing ethoxylated alcohol sulphate and ethoxylated fatty alcohol, which comprises a high concentration of active ingredient, for example about 50 weight percent. Alternatively, there can be more, and there is provided a composition that does not contain a non-detergent active solubilizer or hydrotrope material.

Means for Solving the Problems The above and other objects of the present invention will be more easily apparent from the following description. However, those objects and the preferred embodiments of the present invention include a hydrotropic agent and Replacing the viscosity and transparency control system consisting of a solubilizer with a combination of a relatively lower, eg, about 8 to 10 carbon chain length alcohol sulfate anionic detergent compound and a conventional ethoxylated fatty alcohol nonionic detergent compound, the transparency or Reduce the total cost of the composition without compromising stability, and also
It was realized by the knowledge that it was possible to further raise the total level of active ingredients.

Accordingly, the present invention provides about 15 to about 40 wt% paraffin sulfonate, about 1 to about 10 wt% alkyl ether sulfate having about 12 to 15 carbon atoms in the alkyl chain, an ethoxylated fatty alcohol nonionic detergent. About 2 to about 20% by weight
And a C _{6 to} C ₁₁ alcohol sulfate of from about 0.8 to about 5% by weight, the balance being water, dyes, perfumes, preservatives and other conventional additives in the form of a clear aqueous solution which provides a transparent liquid detergent composition. is there.

The composition of the present invention provides a highly stable, highly foaming cleaner, especially suitable for hand-washing dirty dishes, glassware and tableware.

The water-soluble paraffin sulfonate used in the present invention, which is also called alkane sulfonic acid, is usually a mixed secondary alkyl sulfonate having 10 to 20 carbon atoms per molecule, about 80% or more of which is 12%. From 18 to 18 carbon atoms / molecule or from 10 to 17 carbon atoms / molecule. The preferred range of carbon atom content is 14 to 17 carbon atoms with an average carbon atom content of about 15. Suitable molecular weights are usually in the range 300 to 350.

The paraffin sulfonate is preferably prepared by allowing sulfur dioxide and oxygen to act on the paraffin fraction corresponding to the chain length according to the well-known sulfone oxidation method. The product of this reaction is a secondary sulfonic acid which, when subsequently neutralized with a suitable base, gives a water-soluble 2
A primary alkyl sulfonate is obtained. The other useful secondary alkyl sulfonates can be similarly obtained. For example, the chlorosulfonation technique, in which chlorine and sulfur dioxide are reacted with paraffin in the presence of radiation and the resulting sulfuryl chloride is hydrolyzed and neutralized to form a secondary alkyl sulfonate.

The cations of paraffin sulfonate and the anionic sulfates described below are preferably alkali metals, ammonium or lower alkanolamines. In addition, alkaline earth metals such as magnesium and lower amines are also useful in forming water-soluble detergent salts. Among the alkali metals, the better ones are sodium and potassium, with sodium being preferred. The lower alkanolamine can be any mono-, di- or trialkanolamine containing 1 to 3 carbon atoms in the alkanol group, with ethanolamines such as triethanolamine and diethanolamine being most preferred. Instead of the above, the corresponding amines can also be used. The most preferred paraffin sulfonate is sodium paraffin sulfonate with a substantial (> 80%, preferably> 95%) molecular weight paraffin of about 330.

The amount of paraffin sulfonate in the composition is about 15 to about
It is 40 weight percent, preferably about 25 to 35 weight. At concentrations above 40%, the solubilization of paraffin sulfonates is difficult, even at high levels of nonionic activators and alkyl sulfates, resulting in cloudy compositions at best. If the amount is less than about 15%, the cleaning performance is not sufficient.

The higher alkyl ether sulfate used in the present invention is represented by the chemical formula RO (C ₂ H ₄ O) nSO ₃ M, where R is 10 to 18 carbon atoms,
It is preferably a straight-chain or branched primary or secondary alkyl radical having 12 to 15, particularly preferably 12 to 14, most preferably 12 to 13 carbon atoms, M being suitable as defined for paraffin sulfonates. A positive cation, n
Is 1 to 10, preferably 2 to 6, particularly preferably 2
Or a number of three. This detergent is produced by sulfating the corresponding ether alcohol and subsequently neutralizing the resulting sulfate ester. Particularly preferred are the sodium and ammonium salts of ether sulfates.

The amount of higher alkyl ether sulfate in the composition is about 1
To about 10% by weight, preferably about 2 to about 8% by weight. If the amount of ether sulphate is above or below this range, detergent performance, foaming or stability will not be entirely satisfied.

The nonionic detergent, which is another essential component of the transparent and stable liquid detergent composition of the present invention, cooperates with the alkyl sulfate described below to solubilize the paraffin sulfonate and higher alkyl ether sulfate components. Assists and imparts proper foaming properties as a foam builder. The nonionic detergent also assists in solubilizing the composition at low temperatures. Suitable nonionic activators for use in the present invention include liquid ethoxylated fatty alcohols represented by the structural formula R ¹ O (C ₂ H ₄ O) mH. Wherein R ¹ is a straight or branched chain alkyl containing about 8 to 12 carbon atoms in the molecule,
m is a number on average about 5 to 10, generally about 5 to 8 on average.

Generally, R ¹ will be a mixture of straight chain alkyl groups having a chain length of, for example, 9-11 carbon atoms, 8-10 carbon atoms, 10-12 carbon atoms and the like. Mixed alkyl chain lengths of 9 to 11 carbon atoms are particularly useful. Similarly, the alkyl groups of the ether sulfates will typically be a mixture of carbon chain lengths, usually 80% or more, preferably about 95% or more, falling within the specified range. Nonionic detergents can be distilled, for example, to remove free starting alcohols and lower ethoxylates, and such "distilled" nonionic activators are commercially available.

The amount of nonionic detergent in the composition is about 2 to about 20% by weight, preferably about 5 to about 15% by weight. If the amount of nonionic activator in the composition is less than about 2% by weight, the effect of promoting foaming or solubilizing residual components is hardly observed. on the other hand,
Amounts of nonionic surfactant above about 20% by weight do not significantly improve the cleaning performance and therefore the use of such high contents of nonionic surfactant must be avoided. On the other hand, 2
In the range from 20 to 20% by weight, in particular in the range from 5 to 15% by weight, the presence of the nonionic activator in combination with the alkyl sulphate accelerates the dissolution of the detergent compounds, especially at very high levels of total detergent active ingredients. Allows the formation of clear, stable solutions.

The alkyl sulphate anionic detergent compounds useful according to the invention have 6 to 11 and especially 8 to 10 carbon atoms in the alkyl radical and are represented by the general formula:

R ² SO ₄ M In the above formula, R ² is a straight-chain or branched alkyl with a chain length of 6 to 11, in particular 8 to 10 carbon atoms, and M is as defined above, in particular sodium. Straight chain alkyl groups are preferred.

If the alkyl chain length of the alkyl sulphate is greater than or equal to 12 carbon atoms, for example 12 to 14 carbon atoms, the detergent active compound is particularly high in the total level of detergent active ingredients, for example 40% by weight or more and especially 45% by weight of the total composition. % Or more, it is not completely dissolved and the resulting composition becomes cloudy at room temperature.

In the table below, "EO" represents ethylene oxide. For example, C ₁₂ -C ₁₅ alcohol EO (3: 1) Na sulfate is a condensation product of 1 mol of fatty alcohol sulfate and 3 mol of ethylene oxide, and C ₉ -C ₁₁ fatty alcohol EO (8: 1) refers to the condensation products of C ₉ -C ₁₁ fatty alcohol with 8 moles of ethylene oxide.

For example, the following compositions "A" and "B" were mixed with all the ingredients at room temperature to prepare a total active ingredient concentration of 40 weight percent.

Composition "B" is cloudy, while composition "A" is transparent. Such cloudy compositions are generally unacceptable to consumers, especially when the compositions are provided in clear glass or plastic bottles.

The amount of alkyl sulfate is also important. If the concentration of alkyl sulfate is less than about 0.8 weight percent, the solubilizing effect is insufficient. Whatever the total concentration of detergent active ingredients, if the concentration of alkylsulfate exceeds about 5% by weight, the total detergent performance will deteriorate. Accordingly, the amount of alkyl sulfate anionic detergent component should be in the range of about 0.8 to about 5% by weight, with about 1 to about 3% by weight being preferred.

As mentioned above, a clear aqueous liquid dishwash having a high total level of detergent active compound, in particular having a level of detergent active compound of at least 40% by weight of the total composition, preferably at least about 45% and particularly preferably at least about 50%. It is one of the features of the present invention that a detergent composition can be prepared. About 70% of the total composition weight
Thus, it is possible to prepare clear, stable compositions containing, for example, up to about 65%, in particular from about 50 to about 60% and up to about 60% of a detergent active compound.

The detergent composition of the present invention has a clear point temperature of about 15 ° C (59 ° F) or lower, preferably about 13 ° C (55.5 ° F) or lower.
erature). The clearing point can be easily measured by the following method. The sample composition is prepared and placed in a glass test tube, which is then placed in a freezer (approximately 4
C.) overnight, then remove the test tube from the freezer and raise the temperature at a rate of about 1 C / min. The temperature at which the composition changes from cloudy to clear is the clearing point.

The viscosity of the detergent composition can be further modified by adding thickening agents such as gums and cellulose derivatives. The viscosity and flow characteristics of the product must allow pouring from the bottle, and liquid detergent usage is usually small so it must not be so dilute that the splash or pouring is too easy. Viscosities of 20 to 500 centipoise (Brutsk Field viscometer) have been found to be useful, viscosities of 50 to 300 cps are preferred, and most consumers consider a viscosity of about 200 centimeters to be the best. . A slightly lower viscosity, for example a viscosity of 100 cps, is accepted by consumers almost as well.

The liquid detergents of the present invention may contain any of the additives used to date in other liquid detergent compositions. For example, sequestering agents such as sodium and potassium salts of ethylenediaminetetraacetic acid and salts of hydroxyether ethylenediaminetriacetic acid. In some cases it may also be desirable to color the liquid detergent composition and suitable dyes are used for this purpose. A fragrance may be added to the composition to impart a fragrance. Preservatives, fungicides and the like may be included in the composition.

Water is used in the liquid vehicle of the liquid detergent composition of the present invention. The proportion varies from about 20 to 60 percent depending on the content of other ingredients in the composition.

The composition is generally at neutral pH (7), but a pH of 5-9, preferably 6-8 is also suitable.

Examples The following formulations were prepared to demonstrate the various advantages of the liquid detergent composition of the present invention.

The above conclusions lead to the following conclusions.

Allows the preparation of stable and transparent formulations with useful viscosities over a wide range of active ingredient concentrations, including those where the total active ingredient is greater than 50% by weight.

• At the same level of total active ingredients (52.5% by weight), an increase in the amount of nonionic activator (with a corresponding decrease in paraffin sulfonate) would otherwise clear the hazy composition. Compare experiment 5 (comparative experiment) with experiment 6 (invention).

・ At low levels of about 25% and 30% total active ingredients,
The mixture of paraffin sulfonate and alkyl ether sulphate is at or slightly above the acceptable clearing point boundary. (See Comparative Experiments 7 and 9, respectively.) That is, when the total active ingredient levels were the same at 25% and 30%, a portion of paraffin sulfonate and alkyl ether sulfate was added to the nonionic detergent and lower alkyl. Substitution with sulphate gives a completely acceptable transparent composition, albeit with a relatively low concentration of total active ingredient.
(See Experiments 8 and 10, respectively.) When the amount of lower alkyl sulfate anion detergent approaches 5% by weight (Experiment 11), the clearing point is still acceptable, but the preferred value is about 13 ° C. It is out of the range below.

The compositions of experiments 3, 4 and 11 were tested for cleaning performance of representative formulations of the present invention. For comparison, a composition containing 10% by weight each of paraffin sulfonate, alkyl ether sulfate and alkyl sulfate (Experiment 12) (total active ingredients)
The cleaning performance of 40% by weight, clearing point 7 ° C., viscosity 235 cps) was also measured. This performance test consists of two different water hardnesses, namely
At 50 and 500ppm hardness, each water hardness is 1.25g /
It is a dish-washing test conducted using a detergent concentration of liter.

This dish-washing test was carried out on a uniformly soiled standard dish, and the soiling was obtained by spreading a small amount of commercially available hydrogenated oil and fat (cotton seed oil) on each dish.

The dishes were washed in a dishwashing vessel containing 6 liters of 43 ° C wash water. Each of the test compositions was prepared (at two water hardnesses) and dispensed in separate dishwashing containers. Subsequently, the dishes were washed in the dishwashing container until the end point where the foam covering the dishwashing container was permanently destroyed and the number of dishes washed by that end point was recorded. Differences between the results of the two dishes are generally considered necessary to be significant at 95% confidence. The results below are averages from 3 replicates.

From the above results, it can be seen that although the cleaning performances of Experiments 4 and 11 are very good, the more concentrated composition (Experiment 3) gives the most remarkable cleaning performance. The composition of Experiment 12, which is outside the scope of the present invention, has acceptable transparency and viscosity but poor cleaning performance at both hardness levels.

Experiments 1,2,3,4,6 or 11 in the C ₉ -C ₁₁ fatty alcohol EO8:
Similar results are obtained when C ₉ -C ₁₁ fatty alcohol EO 5: 1 is used instead of 1. Similarly, in any of these compositions, C ₁₂ -C ₁₅ alkyl ether sulfate EO
3: 1, C ₁₂ -C ₁₅ alkyl ether sulfate EO instead of Na salt
Similar results are obtained with 2: 1, Na or ammonium salts.

A clear, stable, yet more viscous composition containing 60% by weight of the active ingredient used in experiments 1, 2, 3, 4, 6 and 11 was prepared.

Paraffin sulfonate 36% Alkyl ether sulphate 6.3% Nonionic activator 15.6% Alkyl sulphate 2.1 All active ingredients 60% Clearing point <13 ° C Viscosity 500cps

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Claims (11)

(57) [Claims] 1. A) 15 to 40% by weight of paraffin sulfonate anionic detergent, (B) 1 to 10% by weight of alkyl ether sulphate anionic detergent in which the alkyl group has 12 to 15 carbon atoms. , (C) 2 to 20% by weight of the chemical formula R ¹ O (C ₂ H ₄ O) _m H, where R ¹ is a straight or branched chain alkyl of 8 to 12 carbon atoms and m is A nonionic detergent which is an ethoxylated fatty alcohol of a number from 5 to 10, (D) 0.8 to 5% by weight of an alkylsulfate anionic detergent in which the alkyl group has 6 to 11 carbon atoms, and (E) ) It contains water, the total of (A), (B), (C) and (D) is 25% by weight or more of the total composition, has a clearing point of 15 ° C or less, and is not a detergent and is soluble. A clear aqueous detergent composition free of agents and hydrotropes. 2. The composition according to claim 1, wherein the total of (A), (B), (C) and (D) is 40% by weight or more of the total composition. 3. The composition according to claim 1, wherein the sum of (A), (B), (C) and (D) is 40 to 60% by weight of the total composition. 4. The composition according to claim 1, wherein the total of (A), (B), (C) and (D) is 50% by weight or more of the total composition. 5. A composition according to claim 1 wherein the paraffin sulfonate has an average of 14 to 17 carbon atoms. 6. An alkyl ether sulfate having a chemical formula of RO (C ₂ H ₄ O) _n SO ₃ M, wherein R is a primary or secondary branched or straight chain having 12 to 14 carbon atoms. An alkyl group, M is an alkali metal, ammonium or lower alkanolamine,
The composition according to claim 1, wherein n is a number from 1 to 10. 7. R is alkyl of 12 to 13 carbon atoms, M
Is sodium or ammonium cation, and
The composition according to claim 6, wherein n is 2 to 6. 8. A method according to claim 1, wherein R ¹ is alkyl having 9 to 11 carbon atoms, and m is a number of 5 to 8.
The composition according to the item. 9. An alkyl sulfate salt having a chemical formula of R ₂ SO ₄ M, wherein R ² is a linear or branched alkyl group having 6 to 11 carbon atoms, and M is an alkali metal, ammonium or lower alkanolamine. The composition of claim 1 which is: 10. The method according to claim 1, which comprises (A) 25 to 35% by weight (B) 2 to 8% by weight (C) 5 to 15% by weight (D) 1 to 3% by weight (E) water. The composition as described. 11. A) 25-35% by weight of C ₁₄ -C ₁₇ paraffin sulfonate, (B) 2-8% by weight of ethylene oxide condensed.
C ₁₂ -C ₁₅ alkyl ether sulphate (molar ratio of the former and the latter is 3: 1), (C) 5-15 wt% condensed with ethylene oxide
C ₉ -C ₁₁ fatty alcohol (the former and the latter ratio is from 8:
The composition according to claim 1, which comprises 1), (D) 1 to 3% by weight of C _{8 to} C ₁₀ alkyl sulfate, and (E) water.